Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate

ABSTRACT

A semiconductor wafer cleaning formulation, including 1-21% wt. fluoride source, 20-55% wt. organic amine(s), 0.5-40% wt. nitrogenous component, e.g., a nitrogen-containing carboxylic acid or an imine, 23-50% wt. water, and 0-21% wt. metal chelating agent(s). The formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.

RELATED APPLICATIONS

THIS APPLICATION is a continuation-in-part CLAIMS THE BENEFIT OF U.S. patent application Ser. No. 08/924,021 FILED ON AUG. 29, 1997 now U.S. Pat. No. 6,224,785, WHICH IN TURN CLAIMS THE PRIORITY OF U.S. PROVISIONAL PATENT APPLICATION 60/044,824 FILED APR. 25, 1997 AND U.S. PROVISIONAL PATENT APPLICATION 60/034,194 FILED JAN. 9, 1997. ADDITIONALLY, THIS APPLICATION CLAIMS PRIORITY TO AND REPEATS A SUBSTANTIAL PORTION OF PRIOR U.S. patent application Ser. No. 08/924,021 FILED ON AUG. 29, 1997. SINCE THIS APPLICATION NAMES AN INVENTOR NAMED IN THE PRIOR APPLICATION, THE APPLICATION CONSTITUTES A CONTINUATION IN PART OF THE PRIOR APPLICATION. THIS APPLICATION INCORPORATES BY REFERENCE PRIOR U.S. patent application Ser. No. 08/924,021 FILED ON AUG. 29, 1997, U.S. PROVISIONAL PATENT APPLICATION 60/044,824 FILED ON APR. 25, 1997 AND U.S. PROVISIONAL PATENT APPLICATION 60/034,194 FILED ON JAN. 9, 1997.

FIELD OF THE INVENTION

The present invention relates generally to chemical formulations useful in semiconductor manufacturing and particularly to chemical formulations that are utilized to remove residue from wafers following a resist plasma ashing step. More specifically, the present invention relates to cleaning formulations for removal of inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.

DESCRIPTION OF THE PRIOR ART

The prior art teaches the utilization of various chemical formulations to remove residues and clean wafers following a resist ashing step. Some of these prior art chemical formulations include akaline compositions containing amines and/or tetraalkyl ammonium hydroxides, water and/or other solvents, and chelating agents. Still other formulations are based on acidic to neutral solutions containing ammonium fluoride.

The various prior art formulations have drawbacks that include unwanted removal of metal or insulator layers and the corrosion of desirable metal layers, particularly copper or copper alloys features. Some prior art formulations employ corrosion inhibiting additives to prevent undesirable copper metal corrosion during the cleaning process. However, conventional corrosion-inhibiting additives typically have detrimental effects on the cleaning process because such additives interact with the residue and inhibit dissolution of such residue into the cleaning fluid. Moreover, conventional additives do not easily rinse off the copper surface after completion of the cleaning process. Such additives therefore remain on the surface sought to be cleaned, and result in contamination of the integrated circuits. Contamination of the integrated circuit can adversely increase the electrical resistance of contaminated areas and cause unpredictable conducting failure within the circuit.

The formulation of post CMP cleaners for advanced integrated circuit manufacturing such as copper and tungsten interconnect materials, includes slurry removal and residue dissolution components that accelerate the physical cleaning process. However, these conventional additives typically have detrimental effects on the metal surface by increasing resistance and corrosion sensitivity.

It is therefore one object of the present invention to provide chemical formulations that effectively remove residue following a resist ashing step, and which do not attack and potentially degrade delicate structures intended to remain on the wafer.

It is another object of the present invention to replace conventional additives with an improved corrosion inhibitor for protection of copper structures on the semiconductor substrate.

It is another object of the invention to provide an improved corrosion inhibitor, which is easily rinsed off the substrate by water or other rinse medium after the completion of the residue-removal process, thereby reducing contamination of the integrated circuit.

Other objects and advantages of the invention will become fully apparent from the ensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

The present invention relates generally to chemical formulations useful in semiconductor manufacturing for removing residue from wafers following a resist plasma ashing step.

In one aspect, the invention relates to a method of removing residue from a wafer following a resist plasma ashing step on such wafer, comprising contacting the wafer with a cleaning formulation, including (i) a fluoride source, (ii) at least one organic amine, (iii) a nitrogen-containing carboxylic acid or an imine, (iv) water, and optionally at least one metal chelating agent.

Another aspect of the invention relates to a wafer cleaning formulation, including (i) a fluoride source, (ii) at least one organic amine, (iii) a nitrogen-containing carboxylic acid or an imine, (iv) water, and optionally at least one metal chelating agent.

In a further aspect, the invention relates to a semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication, comprising the following components in the percentage by weight (based on the total weight of the formulation) ranges shown:

a fluoride source, e.g., ammonium fluoride and/or 1-21% derivative(s) thereof organic amine(s) 20-55%  a nitrogenous component selected from nitrogen-containing 0.5-40%   carboxylic acids and imines water 23-50%  metal chelating agent(s) 0-21% TOTAL 100%

Such formulations of the invention effectively remove inorganic residues following a plasma ashing step.

Such formulations also effectively remove metal halide and metal oxide residues following plasma ashing, and effectively remove slurry particles of aluminum oxides and other oxides remaining after CMP (chemical mechanical polishing).

The formulations of the present invention provide better stripping performance with less corrosivity than formulations containing either ammonium fluoride or amines. Formulations in accordance with the invention also provide better stripping performance at lower processing temperatures than conventional amine-containing formulations.

The formulations of the invention utilize a chelating agent, which may be a single-component chelating agent or a multicomponent chelating agent, to prevent metal corrosion and increase stripping effectiveness.

Other features and advantages of the present invention will be from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a copper-specific corrosion inhibitor useful in the broad practice of the present invention, which forms a protective layer on the copper metal to prevent corrosion;

FIG. 2 is a schematic representation of the copper-specific corrosion inhibitor being rinsed away from the copper surface by deionized water;

FIG. 3 depicts cleaning components of the present invention interacting with a surface;

FIG. 4 illustrates that formulations of the present invention maybe used to remove residues and particles;

FIG. 5 provides a SEM representing results obtained from an immersion process; and

FIG. 6 illustrates the material etch rate on interconnect materials.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The formulations of the present invention are suitable for stripping inorganic wafer residues deriving from high density plasma etching followed by ashing with oxygen-containing plasmas. Such formulations are also suitable for removing slurry particles of aluminum oxides and other oxides remaining after CMP (chemical mechanical polishing).

The formulations advantageously contain (i) a fluoride source, such as ammonium fluoride and/or derivative(s) of ammonium fluoride, (ii) an amine or mixture of amines, (iii) a nitrogen-containing carboxylic acid or imine, (iv) water, and, optionally and preferably, (v) one or more metal chelating agents.

As used herein, a fluoride source refers to a compound or a mixture of compounds that in the aqueous cleaning formulation provides fluorine anions.

The preferred formulations the following components in the percentage by weight (based on the total weight of the formulation) ranges shown:

fluoride source 1-21% organic amine(s) 20-55%  a nitrogenous component selected from nitrogen-containing 0.5-40%   carboxylic acids and imines water 23-50%  metal chelating agent(s) 0-21% TOTAL 100%

The components of the formulation as described above can be of any suitable type or species, as will be appreciated by those of ordinary skill in the art. Specific illustrative and preferred formulation components for each of the ingredients of the formulation are described below.

Particular preferred amines include the following:

diglycolamine (DGA)

methyldiethanolamine (MDEA)

pentamethyldiethylenetriamine (PMDETA)

triethanolamine (TEA)

triethylenediamine (TEDA)

Other amines that are highly advantageous include:

hexamethylenetetramine

3,3-iminobis (N,N-dimethylpropylamine)

monoethanolamine

Specific preferred fluoride sources include:

ammonium fluoride

triethanolammonium fluoride (TEAF)

Other fluoride sources that are highly advantageous include:

diglycolammonium fluoride (DGAF)

tetramethylammonium fluoride (TMAF)

triethylamine tris (hydrogen fluoride) (TREAT-HF)

Specific preferred nitrogen-containing carboxylic acids and imines include:

iminodiacetic acid

glycine

nitrilotriacetic acid

1,1,3,3-tetramethylguanidine

Other nitrogen-containing carboxylic acids or imines advantageously utilizable in formulations of the invention include:

CH₃C(═NCH₂CH₂OH)CH₂C(O)N(CH₃)₂

CH₃C(═NCH₂CH₂OCH₂CH₂OH)CH₂C(O)N(CH₃)₂

CH₃C(═NH)CH₂C(O)CH₃

(CH₃CH₂)₂NC(═NH)N(CH₃CH₂)₂

HOOCCH₂N(CH₃)₂

HOOCCH₂N(CH₃)CH₂COOH

Specific preferred metal chelating agents include:

acetoacetamide

ammonium carbamate

ammonium pyrrolidinedithiocarbamate (APDC)

dimethyl malonate

methyl acetoacetate

N-methyl acetoacetamide

2,4-pentanedione

tetramethylammonium thiobenzoate

tetramethylammonium trifluoroacetate

tetramethylthiuram disulfide (TMTDS)

The combination of ammonium fluoride or a substituted fluoride source, as described above, with an amine (other than an amine present as a surfactant in an amount of 1% or less) provides better stripping performance with less corrosivity than formulations containing either ammonium fluoride or amines alone. In addition, the resulting alkaline solutions are effective at lower processing temperatures (e.g., 21°-40° C.) than conventional amine-containing formulations.

The presence of nitrogen-containing carboxylic acids and/or imines enables formulations of the invention to be remarkably effective in stripping residues from semiconductor substrate surfaces containing delicate copper structures.

The nitrogen-containing carboxylic acids or imines provide functional groups that are specifically attracted to free copper atoms. As shown schematically in FIG. 1, the copper-specific corrosion inhibiting-agent C, while contacts the copper surface during the residue-removal process, will attach to the copper surface and form a protective layer to prevent the copper surface being corroded by cleaning agents A⁺ and X⁻.

Moreover, as shown by FIG. 2, such copper-specific corrosion-inhibiting agent C can be easily rinsed off by deionized water or other solutions and therefore leaves very little contamination on the copper surface after the cleaning operation.

The use of 1,3-dicarbonyl compounds as chelating agents and to prevent metal corrosion is a preferred feature of the inventive formulations, to increase their effectiveness.

In various prior art formulations, amines are present in amounts of 1% or less of the formulation as surfactants, or otherwise are not utilized as formulation ingredients at all. Additionally, the prior art formulations are acidic (pH<7) in character. In preferred formulations of the present invention, the amines are present as major components of the formulation, are highly effective in stripping action, and yield formulations of a basic pH character (pH>7).

The formulations of the invention may include a wide variety of organic amines, substituted ammonium fluorides, and nitrogen-containing carboxylic acids, other than those specifically exemplified. Particular substituted ammonium fluorides of suitable character include those of the general formula, R₁R₂R₃R₄NF in which each of the respective R species is independently selected from hydrogen and aliphatic groups. Suitable nitrogen-containing carboxylic acids include those of the general structure COOH—CH₂—NRR′, wherein R and R′ are each independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acid moieties. Suitable metal chelating agents include 1,3-dicarbonyl compounds of the general structure X—CHR—Y. In compounds of such formula, R is either a hydrogen atom or an aliphatic group, e.g., C₁-C₈ alkyl, aryl, alkenyl, etc. X and Y may be the same as or different from one another, and are functional groups containing multiply-bonded moieties with electron-withdrawing properties, as for example CONH₂, CONHR′, CN, NO₂, SOR′, or SO₂Z, in which R′ represents a C₁-C₈ alkyl group and Z represents another atom or group, e.g., hydrogen, halo or C₁-C₈ alkyl.

Other chelating agent species useful in the compositions of the invention include amine trifluoroacetates of the general formula, R₁R₂R₃R₄N⁺⁻O₂CCF₃ in which each of the R groups is independently selected from hydrogen and aliphatic groups, e.g., C₁-C₈ alkyl, aryl, alkenyl, etc.

The formulations of the invention optionally may also include such components as surfactants, stabilizers, corrosion inhibitors, buffering agents, and co-solvents, as useful or desired in a given end use application of formulations of the invention.

Formulations in accordance with the present invention are particularly useful on wafers that have been etched with chlorine- or fluorine-containing plasmas, followed by oxygen plasma ashing. The residues generated by this type of processing typically contain metal oxides. Such residues are often difficult to dissolve completely without causing corrosion of metal and titanium nitride features required for effective device performance. Also, metal oxide and silicon oxide slurry particles remaining after CMP will also be effectively removed by formulations in accordance with the present invention.

The features and advantages of the invention are more fully shown by the following non-limiting examples.

EXAMPLE 1

Copper-specific corrosion inhibitors including either hydrogen-containing carboxylic acids or imines were tested in two different types of alkaline cleaning formulations, with the following components and characteristics.

TABLE 1 Temp., Copper Etch Components ° C. pH Rate (Å/min) Formulation dimethylacetoacetamide, 70 6.2 17.4 1 amine, and water Formulation ammonium fluoride, 40 8.6 7.5 2 triethanolamine, pentamethdiethylenetriamine, and water

The copper etch rate was determined by a standard four-point probe technique. Addition of corrosion inhibitors in accordance with the present invention significantly slowed down the copper etch rate, as shown by the following table, and effectively prevented undesirable corrosion during the cleaning process:

TABLE 2 Copper Etch Reduction of Temp. Formulation Concentration pH of Rate Etch Rate Corrosion Inhibitor (° C.) Used (%) solution (Å/min) (%) Iminodiacetic Acid 40 2 1.5 8.0 1-2 −73.3˜86.7 Glycine 40 2 1.5 9.2 3.6 −52.0 Nitrilotriacetic Acid 40 2 1.5 8.2 3.6 −52.0 1,1,3,3-tetramethylguanidine 40 2 1.5 8.7 3.4 −54.7 CH₃C(═NCH₂CH₂OH)CH₂ 70 1 24 10.9 6.2 −64.4 C(O)N(CH₃)₂ CH₃C(═NCH₂CH₂OCH₂CH₂OH) 70 1 36 10.7 0.32 −98.2 CH₂C(O)N(CH₃)₂ CH₃C(═NH)CH₂C(O)CH₃ 40 2 13.68 7.9 4.4 −41.3

EXAMPLE 2

A contamination test was carried out on Formulation 2 containing iminodiacetic acid inhibitor. The semiconductor wafer to be cleaned contained copper and silicon films. After the completion of the cleaning operation, the wafer was rinsed by deionized water at 25° C. for about 15 minutes. The Secondary Ion Mass Spectrometry data (SIMS) obtained are as follows:

C Cu_(x)O Cu (atoms/cm²) F (atoms/cm²) (atoms/cm²) (Å) Uncleaned Wafer 1.6 × 10¹⁰ 3.3 × 10¹³ 7.5 × 10¹³ 42 Cleaned Wafer 8.5 × 10⁹  5.1 × 10¹³ 1.5 × 10¹³ 15

The foregoing results show that the copper oxide Cu_(x)O has been effectively removed by the cleaning process, while carbon contamination, which is mainly caused by the organic corrosion inhibitors in the cleaning formulation, has been greatly reduced.

The present invention employs dilute alkaline fluoride in compositions for post CMP cleaning of silicon oxide or aluminum oxide particles from metallic surfaces such as copper or tungsten. FIG. 3 depicts how the cleaning components of the present invention interact with the surface. Specially, FIG. 3 depicts that Alkaline Fluoride 30 and chelating agents 32 dissolving inorganic oxide residues 34 after a CMP process.

FIG. 4 illustrates that the formulations taught by the present invention may be used to remove residues 40 and particles 42 for a copper surface 44. In FIG. 4 particles 42 and residues 40 adhere to metal surface 44 as well as dielectric surface 46. Particles 42 and residues 40 may remain following a CMP process. The chemical solutions of the present invention degrade the attractive forces between the residue and the surface as well as dissolve copper and tungsten oxides and oxy-halides.

Formulations that have been found to be effective in cleaning residue and slurry particles from metal surfaces typically have pH values between about 7 and about 9. These formulations generally are aqueous solutions that comprise a fluoride source, an organic amine, and metal chelating agent. The individual constituents typically constitute a fluoride source and/or a derivative thereof as about 0.1 to about 4.2% of the formulation. The fluoride source may include Ammonium Fluoride, Triethanolammonium Fluoride (TEAF), Diglycolammonium Fluoride (DGAF), Tetramethylammonium Fluoride (TMAF), Ammonium Bifluoride or other such fluoride sources as known to those skilled in the art. The organic Amine or mixture of two amines typically comprises between about 2% and about 11% of the formulation of the present invention, wherein the organic amine can be one of many such organic amines known to those skilled in the art including Methydiethanolamine, Pentamethydiethylenediamine (PMDETA), Triethanolamine (TEA), Monoethanolamine, and Diglycolamine. The metal chelating agent or mixture of chelating agents typically comprises about 0 to about 4.2% of the formulation. Typical metal chelating agent include: iminodiacetic acid, 2,4-pentanedione, methyldiethanolammonium trifluoroacetate, ammonium carbamate, ammonium pyrrolidinedithiocarbamate, ammonium lactate, malonic acid or other similar agents as known to those skilled in the art.

Several representative examples of formulations are:

a. Triethanolamine 4.5% Ammonium Fluoride 0.5% Water 95%  b. PMDETA 3.8-4.5% Ammonium Fluoride 0.5% 2,4-Pentanedione 1%   Water  94-94.7% c. TEA 1.7% PMDETA 1.5% TEAHF 2%   Iminodiacetic Acid 0.4% Ammonium Bifluoride 0.5% Water 93.9%  d. TEA 3.5% PMDETA 1.5% 2,4-Pentanedione   1.35% Ammonium Fluoride 1.2% Water 92.45% e. TEA 7%   PMDETA 3%   2,4-Pentanedione 2.7% Ammonium Fluoride 2.4% Water 84.9% 

Wafers can be immersed in chemical solutions or chemicals can be applied to the wafer surface by spray or through a brush scrubbing system. FIG. 5 depicts a SEM representing the results obtained with a standard immersion process. Specifically FIG. 5 depicts Tungsten plugs after alumina slurry CMP and immersion in formula c for 10 min at 30° C. Furthermore, selectivity to exposed materials may be illustrated by etch rate data. FIG. 6 and table 3 illustrate the material etch rate on interconnect materials including an electroplated copper film.

TABLE 3 Material Etch Rate, Å/min for 21° C. @ 30 min Copper ˜1 Tantalum Nitride <0.1 Titanium <0.1 Titanium Nitride 1.0 Tungsten 0.2 TEOS 1.5 BPSG 4.5

While the invention has been described herein with reference to specific features, aspects, and embodiments, it will be appreciated that the invention is not thus limited. The invention therefore may correspondingly embodied in a wide variety of compositions, with corresponding variations of ingredients, and end use applications. The invention therefore is to be understood as encompassing all such variations, modifications and alternative embodiments, within the spirit and scope of the invention as hereafter claimed. 

What is claimed is:
 1. A semiconductor wafer cleaning formulation, comprising, by weight between about 1% and about 21% fluoride source, between about 20% and about 55% organic amino, between about 23% and about 50% water, a metal chelating agent and between about 0.5% and about 40% of a nitrogenous component including a compound of the formula COOH—CH₂NRR′, wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl and carboxylic acids.
 2. The cleaning formulation of claim 1 wherein said fluoride source comprises a fluoride species selected from the group consisting of: ammonium fluoride; and triethanlammomium fluoride (TEAF).
 3. The cleaning formulation of claim 1 wherein said organic amine(s) comprise an amine selected from the group consisting of: diglycolamine (DGA), methyldiethanolamine (MDEA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA), and triethylenediamine (TEDA).
 4. The cleaning formulation of claim 1 wherein said nitrogenous component includes a species selected from the group consisting of: iminodiacetic acid (IDA); glycine; nitrilotriacetic acid (NTA); and 1,1,3,3-tetramethylguanidine (TMG).
 5. The cleaning formulation of claim 1 including at least one metal chelating agent selected from the group consisting of: acetoacetamide, ammonium carbamate, ammonium pyrrolidinedithiocarbamate (APDC), dimethyl malonate, methyl acetoacetate, N-methyl acetoacetamide, 2,4-pentanedione, tetramethylammonium thiobenzoate, tetramethylammonium trifluoroacetate, and tetramethylthiuram disulfide (TMTDS).
 6. The cleaning formulation of claim 1 wherein said fluoride source comprises a species selected from the group consisting of: ammonium fluoride, triethanolammonium fluoride (TEAF), diglycolammonium fluoride (DGAF), tetramethylammonium fluoride (TMAF), and triethylamine trim (hydrogen fluoride) (TREAT-HF).
 7. The cleaning formulation of claim 1 wherein said organic amine(s) comprises an amine selected from the group consisting of: diglycolamine (DGA), methyldiethanolamine (MDEA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA), triethylenediamine (TEDA), hexamethylenetetramine, 3,3-iminobis (N,N-dimethylpropylamine), and monoethanolamine.
 8. The cleaning formulation of claim 1, wherein said nitrogenous component includes a species from the group consisting of: iminodiacetic acid (IDA) glycine nitrilotriacetic acid (NTA) 1,1,3,-tetramethylguanidine (TMG) CH₃C(═NCH₂CH₂OH)CH₂C(O)N(CH₃)2 CHSC(═NCH₂CH₂OCH₂CH₂OH)CH₂C(O)N(CH₃)₂ CH₃C(═NH)CH₂C(O)CH₃ (CH₃CH₂)₂NC(═NH)N(CH₃CH₂)₂ HOOCCH₂N(CH₃)₂ HOOCCH₂N(CH₃)CH₂COOH.
 9. The cleaning formulation of claim 1 wherein said fluoride source comprises a species selected from the group consisting of: Ammonium fluoride, triethanolammonium fluoride (TEAF), diglycolammonium fluoride (DGAF), tetramethylammonium fluoride (TMAF), and triethylamine tris (hydrogen fluoride) (TREAT-HF); said organic amine(s) comprise a species selected from the group consisting of: diglycolamine (DGA), methyldiethanolamine (MDEA), pentamethyldiethylenetriamine (PMDETA), triethanolamine (TEA), triethylenediamine (TEDA), hexamethylenetetramine, 3,3-iminobis (N,N-dimethylpropylamine), and monoethanolamine; said nitrogenous component comprises a species selected from the group consisting of: iminodiacetic acid (IDA) glycine nitrilotriacetic acid (NTA) 1,1,3,3-tetramethylguanidine (TMG) and maid formulation includes a metal chelating agent comprising a specie, selected from the group consisting of: acetoacetamide, ammonium carbamate, ammonium pyrrolidinedithiocarbamate (APDC), dimethyl malonate, methyl acetoacetate, N-methyl acetoacetamide, 2,4-pentanedion; tetramethylammonium thiobenzoate, tetramethylammonium trifluoroacetate, and tetramethylthiuram disulfide (TMTDS).
 10. The cleaning formulation of claim 1 wherein said fluoride source comprises a compound having the general formula R₁R₂R₃R₄NF in which each of the R groups is independently selected from hydrogen atoms and aliphatic groups, and wherein said formulation includes a metal chelating agent of the formula: X-CHR-Y, in which R is either hydrogen or an aliphatic group and X and Y are functional groups containing multiply bonded moieties having electron-withdrawing properties.
 11. The cleaning formulation of claim 10 wherein each or X and Y is independently selected from CONH₂, CONHR′, CN, NO₂, SOR′, and SO₂Z in which R′ is alkyl and Z is hydrogen, halo, or alkyl.
 12. The cleaning formulation of claim 1 wherein said fluoride source comprises a compound having the formula R₁R₂R₃R₄NF in which each of the R groups is hydrogen or aliphatic, and wherein said formulation includes a metal chelating agent of the formula, R₁R₂R₃R₄N⁺⁻O₂CCF₃ in which each of the R groups is independently hydrogen or aliphatic. 